Fungicidal formulation

ABSTRACT

Adjuvants selectes from mon/ionic water/soluble mixed polyalkoxy-lated aliphatic alcohol surfactants, non ionic water soluble ethoxylated aliphatic alcohol surfactants, amine ethoxylates, and micronized polymeric waxes enhance the efficacy of fungicidal triazolopzrimidines of structural formula I. They can be incorporated into formulations of the fungicidal compounds or be added to spray mixtures (tank mix) as separately formualted additives in order to improve the efficacy and spectrum of these fungicides. This invention also provides fungicidal compositions of said triazolopzrimidines and adjuvants, as well as methods for their use in the control of photopathogenic fungi.

DESCRIPTION

[0001] As a rule, inert carrier ingredients must bei used to bring cropprotection agents, for example, fungicidal compounds, into a form thatthe user can apply them either as such, or after dilution with water.The choice of formulation type and inert ingredients for thatformulation type often determines to a significant extent whether theactie ingredient can display its full activity on application.

[0002] The efficacy of the active components can often be improved byaddition of other (active) ingredients. The observed efficacy of thecombination of ingredients can sometimes be significantly higher thanthat would be expected from the amounts of the individual ingredientsused, thus indicating synergism from the components of the combination.

[0003] The usual components of formulations such as carriers and inertingredient (e.g. organic solvents, suspension agents, emulsion agents,wetting agnets, solubilizing agents) which do not themselves possesspesticidal activity, however, do not usually lead to an unexpectedincrease in efficacy.

[0004] International Patent Application WO 95/01722 discloses pesticidalformulations containing non-ionic surface-active agents which can beselected, inter alia, from liquid polyalkoxylated aliphatic alcohols.However, the addition of these agents is directed to improving thestorage stability of the formulations, and there is no report ofenhancing the activity of fungicides used in the formulations.

[0005] U.S. Pat. No. 4,851,421 discloses the use of polyalkylene-typenon-ionic surface active agents derived from the alkoxylation of fattyalcohols with alkyleneoxides, polyoxyalkylene mono- or dialkylphenyetheror polyoxyalkylene sorbitan fatty acid esters.

[0006] It is an object of this invention to provide methods for furtherenhancement of the efficacy of said fungicidal triazolopyrimidines. Itis another object of this invention to provide fungicidal compositionsof said triazolopyrimidines and adjuvants, as well as methods for theiruse in the control of phytopathogenic fungi.

[0007] There is ongoing research to identify suitable adjuvants whichcombination with the active fungicidal ingredient provide a means tolower the dose of active fungicidal agent required for effective diseasecontrol. This goal is desirable from both an economic and anenvironmental standpoint.

[0008] EP-A 71 792 and EP-A 550 113 disclose fungicidaltriazolopyrimidine compounds. EP-A 943 241 describes the enhancement ofthe fungicidal efficacy of said triazolopyrimidines by the addition ofselected adjuvants from he liqid polyalkoxylated aliphatic alcoholclass.

[0009] It has now been found that the effective amounts of fungicidaltriazolopyrimidines of formula I

[0010] in which

[0011] R¹ and R² independently denote hydrogen or

[0012] C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, orC₄-C₁₀-alkadienyl,

[0013] C₃-C₁₀-cycloalkyl, phenyl, naphthyl, or

[0014] 5- or 6-membered heterocyclyl, containing one to four nitrogenatoms or one to three nitrogen atoms and one sulfur or oxygen atom, or

[0015] 5- or 6-membered heteroaryl, containing one to four nitrogenatoms or one to three nitrogen atoms and one sulfur or oxygen atom, or

[0016] where R¹ and R² radicals may be unsubstituted or may carry one tothree groups R^(a),

[0017] R^(a) is cyano, nitro, hydroxyl, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio,C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy,C₂-C₆-alkynyl, C₃-C₆-alkynyloxy and C₁-C₄-alkylenedioxy; or

[0018] R¹ and R² together with the interjacent nitrogen atom represent a5- or 6-membered heterocyclic ring, containing one to four nitrogenatoms or one to three nitrogen atoms and one sulfur or oxygen atom,which may be substituted by one to three R^(a) radicals;

[0019] R³ represents halogen or C₁-C₆-alkyl or C₁-C₆-alkoxy;

[0020] n represents an integer from 0 to 5; and

[0021] Hal represents halogen;

[0022] which must be applied can be lowered considerably with respect tothe amounts usually employed to achieve the same fungicidal effect, ifthese fungicidal compounds or their formulations are applied incombination with one or more adjuvants selected from the groupsconsisting of

[0023] a) non-ionic water-soluble mixed polyalkoxylated aliphaticalcohol surfactants,

[0024] b) non-ionic water soluble ethoxylated aliphatic alcoholsurfactants,

[0025] c) amine ethoxylates, and

[0026] d) micronized polymeric waxes.

[0027] The biological activity of the active ingredient of formula I canbe increased by including any of these adjuvants in the spray dilutionor directly in the formulation. An adjuvant is defined here as asubstance which can increase the biological activity of an activeingredient but is not itself significantly biologically active. Theadjuvant can either be included in the formulation or can be added tothe spray tank together with the formulation containing the activeingredient. The water-soluble mixed polyalkoxylated or ethoxylatedaliphatic alcohols are particularly useful for liquid formulations, inparticular for aqueous suspension concentrates (SC). The mixedpolyalkoxylated adjuvants are containable by alkoxylation of fattyalcohols having 8-18 C-atoms, with alkylene oxides having 2-6,preferably with a mixture of ethylene oxide and propylene oxide. Thealiphatic moieties of the said fatty alcohols may be straight-chained orbranched. The ethoxy to propoxy ratio is from 50:50 to 90:10. Preferredwater soluble non-ionic surfactants of the mixed alkoxylated aliphaticalcohol class are mixed random or block oligomers of formula II

H₂₊₁C_(n)—O—(CH₂CH₂O)_(x)(CH₂CH(CH₃)O)_(y)H  (II)

[0028] wherein

[0029] n is an integer from 8 to 18;

[0030] x is an integer from 3 to 10; and

[0031] y is an integer from 1 to 3.

[0032] Of particular interest are those water soluble mixedpolyalkoxylated aliphatic alcohols which are commercially availableunder the trademark Plurafac® LF (Tensid-Chemie, Köln/BASF AG,Ludwigshafen). In particular Plurafac® LF 300 has been proven to beespecially advantageous.

[0033] The water soluble polyethoxylated adjuvants are obtainable insimilar fashion and are straight chained or branched CIO-25 alcoholsethoxylated with 10 to 25 ethoxy groups. Particularly preferred isLubrol® 17A17, commercially available from Uniqema, Everberg, Belgium.

[0034] The amine ethoxylate adjuvants are tertiary amine ethoxylatesbased on primary amines such as oleyl amine and tallow amine.Particularly preferred are those comercially available under thetrademark Berol 381® and Berol 303 (Ethomeen® S22) from Akzo NobelSurface chemistry, Sweden.

[0035] A particularly preferred micronized polymeric wax is a modifiedpolyethylene wax commercially available under the trademark ®Ceridust9615A from Clariant GmbH, Augsburg, Germany.

[0036] The enhancement in efficacy by addition of the said adjuvants canbe abserved for the fungicidal triazolopyrimidines of formula I,preferably, wherein

[0037] R¹ and R² together with the adjacent nitrogen atom represent anoptionally substituted 6-membered heterocyclic ring, or wherein R¹represents a C₁₋₆-alkyl, a C₁₋₆-haloalkyl, in particularC₁₋₆-fluoroalkyl, or a C₃₋₈-cycloalkyl group and R² represents ahydrogen atom or a C₁₋₆-alkyl group and/or wherein

[0038] wherein L₁ represents a halogen atom, preferably fluorine orchlorine and L₂ and L₃ each independently represents a hydrogen atom ora halogen atom, preferably fluorine and/or wherein

[0039] Hal represents a chlorine atom.

[0040] In a particularly preferred embodiment the triazolopyrimidine is5-chloro-6-(2-chloro-6-fluorophenyl)-7-N-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-α]pyrimidinecoded compound IA, and5-choro-6-(2,4,6-trifluoro-phenyl)-7-(2,2,2,-trifluoro-1-methyl-amino)[1,2,4]triazolo[1,5-α]pyrimidinecoded compound IB.

[0041] The adjuvants of the present invention can be included in theformulation or added in a suitable form with the preparation of thespray mix (tank mix). In this latter case, they are added preferably asa separate preparation with the other components such as a dispersingagent or an antifoam and, where desirable, with further adjuvants so asto ensure that they are homogenously dispersed in the spray mix.

[0042] The present invention also relates to fungicidal formulatiomswith at least mone compound of formula I, adjuvants and/or carriersubstances characterised by their containing, in addition to theconventional adjuvants and carriers, one ore more adjuvants selectedform the group consisting of

[0043] a) non ionic water-soluble mixed polyalkoxylated aliphaticalcohol surfactants,

[0044] b) non-ionic water soluble ethoxylated aliphatc alcoholsurfactants,

[0045] c) amine ethoxylates, and

[0046] d) micronized polymeric waxes.

[0047] The fungicidal compounds can be applied as normal commercialformulations with adjuvants accoring to the invention, and wheredesirable, with additional components such as antioxidants and emulsionagents.

[0048] The appropiate relative amounts of active ingredient and thewater-soluble adjuvant lie, in accordance with the invention, between100:75 and 100:100,000, preferably between 100:90 and 100:50,000 and,more preferably, between 100:125 and 100:5,000. In general and withincertain limits, the fungicidal efficacy can be enhanced to a higherdegree by the addition of larger amounts of the adjuvant.

[0049] In a preferred embodiment the adjuvant is added to the tank mixtogether with the triazolopyrimidine as a formulation.

[0050] The present invention also relates to a kit for the preparationof a spray mixture consisting of two separate containment:

[0051] 1) a containment which comprises at least one fungicide offormula I and conventional inert ingredients and carriers;

[0052] 2) a containment which comprises at least one adjuvant selectedfrom the group consisting of

[0053] a) non-ionic water-soluble mixed polyalkoxylated aliphaticalcohol surfactants,

[0054] b) non-ionic water soluble ethoxylated aliphatic alcoholsurfactants,

[0055] c) amine ethoxylates, and

[0056] d) micronized polymeric wax.

[0057] In a preferred embodiment said kit will consist of two bottleswith dispensing means which allow the easy and correct addition of theactive ingredient (1) and the adjuvant (2) to the tank mix.

[0058] Recommended doses for various applications are known for thefungicidal compounds of formula I where the efficacy can be enhanced inaccordance with the invention. Addition of the adjuvants suggested herecan (depending on the active ingredient, the adjuvant and their amounts)reduce the amount of active ingredient per hectare required in theserecommendations by half or more, whereby it becomes possible to controladditional diseases at reasonable doses.

[0059] In a preferred embodiment the adjuvants in combination with thefungicide of formula I are applied at rates of 40 to 4000 ml/ha,preferably 50 to 3000 ml/ha, in particular 60 to 2000 ml/ha.

[0060] An important advantage is the rapid onset and the highpersistency of activity on use of the new additives. This enlarges theperiad for application of the fungicide and, hence, makes it moreuseful.

[0061] The fungicidal formulations according to the present inventioncan be used in combination with said additives prophylactically andcuratively.

[0062] The adjuvants according to the invention, the compounds offormula I, and usual adjuvants and carriers can be processed to thepreferably fluid or dispersible solid formulations known in the art, forexample, as solutions, emulsions, wettable powders (WPs), suspensionconcentrates (SCs), emulsion concentrates (ECs), low volume or ultra lowvolume preparations and water dispersible granules (WGs).

[0063] As well as fluid and/or solid carries or solubilising agents suchas organig solvents like ketones, alcohols, fluid aliphatic, aliphaticor aromatic compounds, fine natural or synthetic silicates orcarbonates, the preparations usually contain ionic and/or non-ionicsurfactants which function as emulsion, dispersing or wetting agents.Antifoam and antifreeze agents may also be added. Suitable adjuvant andcarriers substances are described in the literature and well known tothe persons skilled in the art.

[0064] A composition according to the invention preferably contains from0.5% to 95% by weight (w/w) of active ingredient.

[0065] A carrier in a composition according to the invention is anymaterial with which the active ingredient is formulated to facilitateapplication to the locus to be treated, which may for example be aplant, seed or soil, or to facilitate storage, transport or handling. Acarrier may be a solied or a liquid, including material which isnormally a gas but which has been compressed to form a liquid.

[0066] Aqueous dispersions and emulsions, for example compositionsobtained by diluting the formulated product according to the inventionwith water, also lie within the scope of the invention.

[0067] Of particular interest in enhancing the duration of theprotective activity of the compounds of this invention is the use of acarrier which will provide slow release of the pesticidal compounds intothe environment of a plant which is to be protected.

[0068] Examples of formulations according to the invention are shown inthe following formulations A and B:

[0069] Formulation A: Suspension Concentrate (SC) Component Amount [g/l]Ingredient active ingredient 200.0 Compound TA dispersant 30.0 Morwet ®D425¹ dispersant 15.0 Pluronic ® PE 10500² antifoam agent 2.0Rhodorsil ® 426 R³ structure agent 1.0 Rhodopol ® 23³ preservative 2.0Proxel ® GXL⁴ structure agent 5.0 Veegum T⁵ antifreeze agent 40.0propylene glycol water to 1000 ml

[0070] The SC formulation described above is mixed before applcationwith water to give a spray mix with the desired concentration of activeingredient. A non-ionic surface-active agent selected from thewater-soluble mixed polyalkoxylated aliphatic alcohol class, inparticular Plurafac® LF300 (250 g/l), is added to the resulting tankmix.

[0071] Formulation B: Suspension Concentrate (SC) Component Amount [g/l]Ingredient active ingredient 200.0 Compound IA dispersant 30.0 Morwet ®D425¹ dispersant 15.0 Pluronic ® PE 10500² preservative 2.0 Proxel ®GXL³ antifoam agent 5.0 SAG 220¹ structure agent 0.8 Rhodopol ® 23⁴structure agent 5.0 Vegum Pro⁵ water to 1000 ml

[0072] The SC formulation described above is mixed before applicationwith water to give a spray mix with the desired concentration of activeingredient. A non-ionic surface-active agent selected from thewater-soluble mixed polyalkoxylated aliphatic alcohols, in particularPlurafac® LF 300 (150 g/l) and additionally a non-ionic surface-activeagent selected from the water soluble polyethoxylated aliphatic alcoholclass, in particular Lubrol 17A17 (150 g/l) is added to the resultingtank mix.

[0073] It is also an object of the invention to suggest a method for thecontrol of phytopathogenic fungi, characterised by the use of thecompounds of formula I, in particular formular IA in combination withone or more adjuvants selected from the groups consisting of

[0074] a) non-ionic water-soluble mixed polyalkoxylated aliphaticalcohol surfactants,

[0075] b) non-ionic water soluble ethoxylated aliphatic alcoholsurfactants,

[0076] c) amine ethoxylates, and

[0077] d) micronized polymeric waxes.

[0078] Plant diseases that can be combated with the fungicidalformulations according to the present invention diseases caused byAscomycete fungi, such as Erysiphales as for example Erysiphecichoracearum or Uncinula necator, and Dothideals as for exampleVenturia inaequalis or Septoria tritici (Mycosphaerella gramini-cola).

[0079] For a more clear understanding of the invention, specificexamples thereof are set forth below.

[0080] The test results described below demonstrate the enhancement infungicidal efficacy of triazolopyrimidines of formula I by the additionof adjuvants according to the invention.

EXAMPLE 1

[0081] Greenhouse Evaluations for Curative and Residual FungicidalActivity

[0082] The formulated compound (see formulation below) was prepared asan aqueous suspension using concentrations of 100, 20 and 4 ppm activeingredient (a.i.) and was applied to greenhouse plants using asingle-nozzle overhead rack sprayer at an application rate of 200litre/ha. Within the 200 l/ha the compound was alternatively in-tankmixed with 1000 ppm of adjuvant(s) (as given in tale of results). Incase two adjuvants were added to the compound, the concentration of eachadjuvant was 500 ppm.

[0083] Barley seedlings (var. ‘Golden Promise’) and wheat seedlings(var. ‘Kanzler’) were grown to the primary leaf stage (ca. 1 week old)in 6-cm-diameter pots in the greenhouse. Plants for both curative andresidual tests were sprayed at the same time with inoculations of thepathogens being done in different days.

[0084] For curative tests, barley and wheat plants were inoculated 2days prior to compound treatment by dusting with conidia of Blumeria(Erysiphe) graminis f.sp. hordei or B. graminis f.sp. tritici to createpowdery mildew diseases. Plants were kept in the greenhouse untiltreated. After tratment, the plants were returned to the greenhouse andkept there until powdery mildew disease symptoms/signs developed onuntreated plants.

[0085] Plants were than evaluated for percent disease on the treatedprimary leaves. For curative rust tests, wheat plants were inoculated 2days prior to compound treatment by spraying with a urediniosporesuspension in 0.05% aqueous Tween 10 (1 mg spores per 40 ml) of Pucciniarecondita, kept in a moist infection chamber for one day then moved tothe greenhouse until treated. After treatment the plants were kept inthe greenhouse until disease symtoms/signs developed on a untreatedplants. Plants were then evaluated for percent disease on the treatedprimary leaves.

[0086] For residual tests, plants were treated first and then kept for 4days in the greenhouse before being inoculated with the pathogens asdescribed for curatuve tests. Inoculated plantes were kept in thegreenhouse until desease symptoms/signs develop on untreated plants.Plants were the evaluated for percent desease on the treated primaryleaves.

[0087] Disease control efficacy was calculated from the percent diseasevalues using the following formula:${\% \quad {disease}\quad {control}} = {100 - \frac{\% \quad {infected}\quad {leaf}\quad {area}\quad {in}\quad {treated}\quad {plants}}{\% \quad {infected}\quad {leaf}\quad {area}\quad {in}\quad {{un}{treated}}\quad {plants}}}$

[0088] Table I gives the means of the efficacy (%control) of the threeconcentrations of compound IA used. This is accepted because theadjuvant concentrations were the same at all the compound a.i.concentrations used.

[0089] The composition of formulation R in Table I is

[0090] Formulation R: Suspension Concentrate (SC) Component Amount [g/l]Ingredient active ingredient 100.0 Compound IA dispersant 20.0 AtlasG5000¹ dispersant 10.0 Synperonic A¹ antifoam agent 3.0 Rhodorsil ® 426²preservative 2.0 Proxel ® GXL³ structure agent 3.0 Rhodopol ® 23²antifreeze agent 50.0 propylene glycol water to 1000 ml

[0091] TABLE I Mean % Control Over 3 Rates (100-20-4 ppm) of Compound 1AWPM* WLR* BPM* 2 Day 4 Day 2 Day 4 Day 2 Day 4 Day Treatment CurativeResidual Curative Residual Curative Residual Formulation A 16 42 48 1021 14 Formulation A & Pluarafac LF 300 49 40 69 28 69 30 (1000 ppm)Formulation A & Lubrol 17A17 43 33 72 15 38 26 (1000 ppm) Formulation A& Pluarafac LF 700 42 40 79 33 38 28 (500 ppm) + Lubrol 17A17 (500 ppm)Formulation A & Pluarafac LF 300 55 49 78 38 57 43 (500 ppm) + Lubrol17A17 (500 ppm) Formulation A & Berol 381 52 47 72 23 54 38 (1000 ppm)Formulation A & Ethimeen S 22 53 48 72 22 56 28 (1000 ppm) Formulation A& Ceridust 9615 A 29 45 62 27 35 32

1. An aqueous suspension concentrate (SC) comprising at least onetriazolopyrimidine of formula I

in which R¹ and R² independently denote hydrogen or C₁-C₁₀-alkyl,C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, or C₄-C₁₀O-alkadienyl,C₃-C₁₀-cycloalkyl, phenyl, naphthyl, or 5- or 6-membered heterocyclyl,containing one to four nitrogen atoms or one to three nitrogen atoms andone sulfur or oxygen atom, or 5- or 6-membered heteroaryl, containingone to four nitrogen atoms or one to three nitrogen atoms and one sulfuror oxygen atom, or where R¹ and R² radicals may be unsubstituted or maycarry one to three groups R^(a), R^(a) is cyano, nitro, hydroxyl,C₁-C₆-alkyl, C₁-C₆-halo-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, C₂-C₆-alkynyl,C₃-C₆-alkynyloxy and C₁-C₄-alkylenedioxy; or R¹ and R² together with theinterjacent nitrogen atom represent a 5- or 6-membered heterocyclicring, containing one to four nitrogen atoms or one to three nitrogenatoms and one sulfur or oxygen atom, which may be substituted by one tothree R^(a) radicals; R³ represents halogen or C₁-C₆-alkyl orC₁-C₆-alkoxy; n represents an integer from 0 to 5; and Hal representshalogen together with one or more adjuvants selected from (a) non-ionicwater-soluble mixed polyalkoxylated aliphatic alcohol surfactants whichis a random or block oligomer of formula IIH_(2n+1)C_(n)—O—(CH₂CH₂O)_(x)(CH₂CH(CH₃)O)_(y)H  (II)  wherein n is aninteger from 8 to 18; x is an integer from 3 to 10; y is an integer from1 to 3; and (b) non-ionic water soluble ethoxylated aliphatic alcoholsurfactants, the adjuvant is present in an amount sufficient to providea ratio of the compound of formula I to adjuvant at 100:75 to 100:100000in the applied formulation.
 2. The formulation according to claim 1,wherein the adjuvant is a surfactant (a).
 3. The formulation accordingto claims 1 or 2 comprising an additional fungicidal compound.
 4. Theformulation according to claims 1 to 3, wherein the relative proportionof the triazolopyrimidine of formula I to the adjuvant is from 100:90 to100:50000.
 5. The formulation according to claim 1 to 4, wherein therelative proportion of the triazolopyrimidine of formula I to saidadjuvant is from 100:125 to 100:5000.